A mononuclear non-heme manganese(IV)-oxo complex binding redox-inactive metal ions

Junying Chen, Yong Min Lee, Katherine M. Davis, Xiujuan Wu, Mi Sook Seo, Kyung Bin Cho, Heejung Yoon, Young Jun Park, Shunichi Fukuzumi, Yulia N. Pushkar, Wonwoo Nam

Research output: Contribution to journalArticlepeer-review

165 Scopus citations


Redox-inactive metal ions play pivotal roles in regulating the reactivities of high-valent metal-oxo species in a variety of enzymatic and chemical reactions. A mononuclear non-heme Mn(IV)-oxo complex bearing a pentadentate N5 ligand has been synthesized and used in the synthesis of a Mn(IV)-oxo complex binding scandium ions. The Mn(IV)-oxo complexes were characterized with various spectroscopic methods. The reactivities of the Mn(IV)-oxo complex are markedly influenced by binding of Sc3+ ions in oxidation reactions, such as a ∼2200-fold increase in the rate of oxidation of thioanisole (i.e., oxygen atom transfer) but a ∼180-fold decrease in the rate of C-H bond activation of 1,4-cyclohexadiene (i.e., hydrogen atom transfer). The present results provide the first example of a non-heme Mn(IV)-oxo complex binding redox-inactive metal ions that shows a contrasting effect of the redox-inactive metal ions on the reactivities of metal-oxo species in the oxygen atom transfer and hydrogen atom transfer reactions.

Original languageEnglish
Pages (from-to)6388-6391
Number of pages4
JournalJournal of the American Chemical Society
Issue number17
StatePublished - 1 May 2013


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